Esters of thiophene-modified copolymers of maleic anhydride with aliphatic vinyl compounds



Patented Mar. 9, 1954 UNlTED STATES PATENT ESTERS F THIOPHENE-MODIFIED CO- POLYMERS OF MALEIC ANHYDRIDE WITH ALIPHATIC VINYL COMPOUNDS John J. Giammaria, Woodbury, N. J assignor to Socony-Vacuum Oil Company, Incorporated, a corporation 01 New York OFFICE No Drawing. Original application November 14,

1949, Serial No. 127,267. Divided and this application April 3, 1951, Serial No. 219,123

7 Claims. (Cl. 260-785) ing alcohol and amine derivatives of thiophenemodified copolymers of maleic anhydride and aliphatic vinyl compounds.

The copolymerization of maleic anhydride with various aliphatic vinyl compounds has been shown in the prior art. The esterification of the that these thiophene-modified polymers may be reacted with relatively long-chain, primary, normal, aliphatic alcohols to form esters, or with relatively long-chain, aliphatic, primary or secondary amines to form amides or imides; and that the derivatives so produced are efl'ective viscosity index improvers and pour point depressants for lubricating oils. It is, therefore, the primary object of this invention to provide a method for producing such thiophene-modified copolymers and alcohol and amine derivatives thereof.

It is a further object to provide improved lubricating oil compositions containing alcohol and amine derivatives of the said thiophene-modified copolymers. Other objects will be apparent from the following detailed description of the invention.

As already indicated, the copolymers and alcohol and/0r amine derivatives thereof contem- 2 ny1 butyl ether, vinyl octyl ether, vinyl dodecyl ether, vinyl tetradecyl ether, vinyl hexadecyl ether, vinyl octadecyl ether, vinyl octenyl ether, vinyl tetradecenyl ether, vinyl octadecenyl ether; (b) Vinyl esters, such as vinyl acetate, vinyl butyrate, vinyl caprylate, vinyl caprate, vinyl .laurate, vinyl myristate, vinyl palmitate, vinyl stearate; l

(0) Acrylic esters, such as ethyl acrylate, prop lymer products with alcohols and amines has 10 pyl acrylate, amyl acrylate, heptyl acrylate, nonyl also been show o insofar as is known, acrylate, undecyl acrylate, tetradecyl acrylate, the copolymerization has never been carried out hexadecyl acrylate, octadecyl acrylate, ethenyl in the presence of thiophene, or an alkyl th-ioacrylate, dodecenyl acrylate, octadecenyl acryphene, to produce a thiophene-containing polyl te; mer roduct, (d) Allyl esters, such as allyl acetate, allyl bu- I have now found that the cOD ly e P tyrate, allyl caprylate, allyl caprate, allyl laurate, duced by copolymerizing maleic anhydride with allyl myristate, allyl palmitate, allyl stearate;

an aliphatic vinyl compound, such as a vinyl (e) Allyl ethers, such as allyl ethyl ether, allyl ester, vinyl ether, acry c ester, allyl ether, allyl W octyl ether, allyl dodecyl ether, allyl tetradecyl ester or an alpha-olefin, in the presence of thioether, allyl hexadecyl ether, allyl octadecyl ether, Dhene or an alkyl-su s t op e Contain allyl ethenyl ether, allyl octenyl ether, allyl tetraappreciable amounts of sulfur, as the result of decenyl ether, allyl octadecenyl ether; the interaction of the thiophene compound with (f) Alpha-olefins, such as ethylene, propylene, the other two reactants. I have further found a; butane-1, t -1, d d c n -1, t t d q hexadecene-l and heptadecene-l.

reactants may be heated together, either in bulk plated h r in ar prepared y first p ly i or in the presence of a suitable solvent, such as ing maleic anhyd de w th an aliphatic v yl xylene, at temperatures ranging from about p n i e p n f i p n r n 0'. to about C. A polymerization catalyst alkyl thiophene, and than i yine' t e nte of the peroxide type, such as benzoyl peroxide, is polymer product with an alcohol or amine, par- 5 preferably used. The reaction time varies from ticularly an aliphatic alcohol or amine.

As non-limiting examples of the aliphatic vinyl compounds suitable for use in the polymerization reaction, the following may be mentioned:

(a) Vinyl ethers, such as vinyl ethyl ether, vi-

about 15 minutes to about 10 hours, although the reaction is usually completed in from about 1 to about 5 hours.

The amount of thiophene, or alkyl-substituted thiophene, used may be varied over wide limits.

3 Thus, as little as 0.25 mol of thiophene for each mol of maleic anhydride and vinyl compound may be used, or the amounts may be increased to solvent proportions, such as from 2 to 6 mols per mol of maleic anhydride and vinyl compound. In general, it is preferred to use equimolar quantitles of all three reactants, since in this proportion higher yields of modified copolymers, which still contain amounts of sulfur in the order of 3 to 4 weight per cent, are obtained.

dimethylitaconate copolymer, thiophene-modified maleic anhydride allyl acetate copolymer,

have also found that when these copolymers are esterified with relatively pure, primary, normal alcohols containing 14 to 16 carbon atoms or with a mixture of such alcohols containing an average of about 14 carbon atoms, such as Lorol-B," they function as pour point depressants as well as viscosity index improvers.

Amines suitable for reaction with the thio-' I phene-modified copolymers to give the products methyl thiophene-modified maleic anhydrideallyl laurate copolymer, thiophene-modified maleic anhydride-allyl palmitate copolymer, tributyl thiophene-modified maleic anhydride-allyl ethyl ether copolymer, 3-methyl thiophenemodified maleic anhydride-allyl octyl ether copolymer, tetrabutyl thiophene-modified maleic anhydride-allyl hexadecyl ether copolymer, thiophene-modified maleic anhydride-ethylenecopolymer and 1 methyl-thiophene-modified maleic anhydride-octadecene-i copolymer.

Alcohols suitable for esterifying the heteropolymers herein contemplated comprise primary,

normal, aliphatic alcohols having from about 12 to about 18 carbon atoms. Suitable alcohols are, for example, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol,

dodecenyl alcohol, tetradecenyl alcohol and octah decenyl alcohol.

Mixtures of primary, normal, aliphatic alcohols having an average of 12 to 14 carbon atoms per molecule may also be used. Such mixtures of alcohols are represented by those marketed by E. O. Du Pont de Nemours & Co. under the trade names Lorol-B and Lorol-5. These alcohol mixtures contain primary, normal, aliphatic alcohols, ranging from 10 to 18 carbon atoms, in approximately the following proportions:

fulfil Bl! l|I r0l 5II 2. 5 2. 8 55. 0 6i. 0 20. 5 21. 0 9. 0 ll. 0 l3. 0. 2. 2

Ave. No. C Atoms l3. 5 12. 7

contemplated herein include aliphatic, primary amines containing from 12 to 18 carbon atoms or the corresponding secondary amines. Such amines are available from Armour and Co. under the "Armeen trade name. As examples of specific suitable amines there may be mentioned: lauryl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, dihexyl amine, diheptyl amine. dioctyl amine, dinonyl amine and methyldecyl amine. A mixture of amines containing 8 to 18 carbon atoms and an average of about 12 carbon atoms per molecule, designated "Armeen CD, may also be used.

The reaction of the modified copolymers with the alcohols or amines to form esters, imides and amides may be carried out by any of the wellknown standard esterification procedures. Thus, for example, the thiophene-modifled copolymers and the alcohol, or amine, may be mixed together and heated in the presence of a catalyst such as sulfuric acid. A solvent medium. such as xylene, may be used if desired.

Typical examples of modified copolymeralcohol and amine derivatives contemplated herein are the following: the lauryl ester of thiophene-modified maleic anhydride-vinyl acetate copolymer, the tetradecyl ester of thiophenemodifled maleic anhydride-vinyl caprylate copolymer, the lauryl amine derivative of 3-methyl thiophene-modified maleic anhydride-vinyl laurate copolymer, the tetradecyl ester of wax-thiophene-modifled maleic anhydride-vinyl ethyl ether copolymer, the tetradecyl amine derivative of dibutyl thiophene-modified maleic anhydridevinyl octyl ether copolymer, the tetradecyl ester of tetrabutyl thiophene-modified maleic anhydride-vinyl acetate copolymer, the octadecyl ester of thiophene-modified maleic anhydrideethyl acrylate copolymer, the tetradecyl ester of diwax thiophene-modified maleic anhydrideoctadecenyl acrylate copolymer, the octadecyl ester of 2-octadecy1 thiophene-modified maleic anhydride-allyl acetate copolymer, the Lorol-B" ester of S-methyl thiophene-modiiied maleic anhydride-allyl stearate copolymer, the Lorol-5" ester of thiophene-modified maleic anhydrideallyl octadecenyl ether copolymer, the tetradecyl ester of 3-methyl thiophenamodified maleic anhydride-allyl tetradecyl ether copolymer, the "Lorol-B ester of thiophene-modified maleic anhydride-ethylene copolymer, and the hexadecyl ester of l-methyl thiophene-modified maleic anhydride-octadecene copolymer.

The following examples serve to illustrate the detailed preparation of a number of the products contemplated herein.

EXAMIPLEI Thiophene-modifled maleic anhydride-vinyl vacetate copolymer Forty-nine grams of maleic anhydride (0.5 mole), 43.0 grams of freshly distilled vinyl acetate (0.5 mole), 1.0 gram of benzoyl peroxide and 240.0 cc. of thiophene (3.0 moles) were mixed and heated to 84 C. while stirring to obtain complete solution. Heating at this temperature was continued for hours during which time'a brown resinous material was precipitated on the wall of the reaction flask. The clear liquid portion was decanted and the residue was dissolved in acetone. The acetone solution was poured into benzene to reprecipitate the modified copolymer which was separated by vacuum filtering and dried to a light brown powder. This modified copolymer contained 10.3% sulfur.

EXAMPLEII S-methyl thiophene-modified maleic anhydridevinyl acetate copolymer Twenty-four and one-half grams of maleic anhydride (0.25 mole), 21.5 grams of freshly distilled vinyl acetate (0.25 mole), 0.12 gram of benzoyl peroxide and 180.0 cc. of 3-methyl thiophene (1.9 moles) were mixed and heated to 108 C. The solution gradually became cloudy. Heating at this temperature was continued for 3 hours, the modified copolymer precipitating as a yellow solid on the walls of the reaction vessel. Themixture was cooled, the liquid portion decanted and the modified copolymer was purified as described in Example I. This modified copolymer contained 13.2% sulfur.

EXAMPLE III 3-methyl thiophene-modified maleic anhydridevinyl acetate copolymer (1 :1 mole ratio) Twenty-four and one-half grams of maleic anhydride (0.25 mole), 21.5 grams of freshly distilled vinyl acetate (0.25 mole), 24.5 grams of 3-methyl thiophene 0.25 mole), 1.0 gram of benzoyl peroxide and 200.0 cc. of xylene were mixed and slowly heated to 110 C. After heating at this temperature for 1 hours, the precipitated modified copolymer was purified by dissolving in acetone and reprecipitating by pouring this solution into cold water. The modified copolymer was filtered off and dried to a light brown powder which contained 5.4% sulfur.

EXAIWPLE IV Thiophene-modified malez'c anhydride-vinyl acetate copolymer (1:1 mole ratio) Ninety-eight grams of maleic anhydride (1.0 mole) 86.0 grams of freshly distilled vinyl acetate (1.0 mole) 84.0 grams of thiophene (1.0 mole), 2.8 grams of benzoyl peroxide and 500.0 cc. of xylene were mixed and slowly heated to 108 C. Heating was discontinued due to vigorous refluxing. As the temperature subsided, the reaction mixture was again heated to 108 C. and held for 1 hour. The mixture was then cooled and the precipitated modified copolymer was filtered oil and dried at 100 C. in a vacuum oven. The dried modified copolymer was a very fine powder containing 3.7% sulfur.

EXAMPLE V Thiophene-modified maleic anhydride-vinyl acetate copolymer (.5:1 mole ratio) A modified copolymer was prepared as described in Example IV except that one-half the amount of thiophene was used and the xylene solvent was omitted. This modified copolymer still contained 3.3% sulfur.

6 EXAMPLEVI Thtophene-modified malez'c anhydride-vinyl butyl ether copolymer Sixteen and one-half grams of freshly distilled vinyl butyl ether (0.165 mole), 16.5 grams of maleic anhydride (0.17 mole), 1.2 grams of benzoyl peroxide and cc. of thiophene were mixed and heated at reflux for 5 hours.

The precipitated modified copolymer was purified as described in Example I and contained 5.8% sulfur.

EXAMPLE VII Thiophene-modified maleic anhydride-octene-1 copolymer Forty-six grams of octene-l (0.5 mole), 49.0 grams of maleic anhydride (0.5 mole), 42.0 grams of thiophene (0.5 mole) and 1.5 grams of benzoyl peroxide were mixed and slowly heated to 105 C. After heating for :1 hour at this temperature, the mixture was cooled and the modified copolymer purified as described in Example I. The modified copolymer contained 5.5% sulfur.

EXAMPLE VIII Lauryl ester of 3-methyl thiophene-modified male c anhydride-vinyl acetate copolymer Ten grams of the modified copolymer from Example III, 50.0 grams of lauryl alcohol (Eastman Kodak's technical grade), 0.5 cc. of concentrated H2804 and 100 cc. of xylene were mixed and heated to reflux in a flask equipped with a Dean-Stark moisture trap for separating the water formed during esterificatlon. After refluxing for four hours, the xylene was gradually distilled whereby the temperature was finally raised to C. The viscous residue was cooled, dissolved in benzene and filtered. The benzene was then removed by distillation followed by heating to 260 C. under 1 mm. vacuum to remove excess alcohol. The very viscous ester modified copolymer thus obtained (Product VIII) contained 2.2% sulfur and was readily soluble in lubricating oil.

EXAMPLE IX Laur Z ester of thiophene-modified maleic anhydride-vinyl acetate copolymer EXAMPLE X Ca'tyl ester of thiophene-modified maleic anhydride-vinyl acetate copolymer Ten grams of the modified copolymer from Example IV, 40.0 grams of n-cetyl alcohol, 0.5 cc. of concentrated H2SO4 and 100 cc. of xylene were mixed and treated as in Example IX. This product was designated as Product X.

EXAMPLE XI Octadecyl ester of thiophene-modified maleic anhydride-vinyl acetate copolymer Ten grams of the modified copolymer from Example IV, 40.0 grams of n-octadecyl alcohol,

0.5 cc. concentrated H2804 and 100 cc. of xylene were mixed and treated as in Example VIII. The ester copolymer (Product In) contained 0.81% sulfur and was readily soluble in lubricating oil.

EXAMPLE XII "Lorol-B" ester of thiophene-modified maleic anhydride-vinyl butvl ether copolymer F'our grams of the modified copolymer from Example VI, 20.0 grams of Lorol-B," 0.2 gram of p-toluene sulfonic acid and 100 cc. of toluene were mixed and treated as described in Example VIII. The ester copolymer (Product XII) contained 2.32% sulfur and was readily soluble in lubricating oil.

EXAMPLE XIII Lorol-B" ester of thiophene-mod fied maleic anhydride-octene-l copolymer Fifteen grams of the modified copolymer from Example VII, 34.0 grams of Lorol-B, 0.3 cc. of

' concentrated H2804 and 100 cc. of xylene were mixed and treated as described in Example IX. The ester copolymer (Product XIII) contained 1.54% sulfur and was readily soluble-in lubricating oil.

EXANDLE XIV Di-octadecul amine derivative of thiophenemodifled maleic anhydride-vinyl acetate copolymer Five grams of the modified copolymer from Example IV, 30.0 grams of di-octadecylamine (Armours Am-2l80) and 150 cc. of xylene were mixed and heated at reflux for 3 hours in a flask equipped with a Dean-Stark moisturetrap for separating the water of reaction. Xylene was gradually removed by distillation whereby the temperature was finally raised to 200 C. The product was cooled and extracted several times with 100 cc. portions of hot ethyl alcohol to remove unreacted amine. The residue (Product XIV) after evaporation of entrained alcohol analyzed 2.26% N.

Pour point depression The efiectiveness of the products described herein as pour point depressants is illustrated by the data presented in Table I. The results were obtained in a Duo-sol refined, Mid-Continent type base oil having a kinematic viscosity of 12.2 centistokes at 210 F. and an A. S. T. M. pour point of +20 F.

V. I. improvement The effectiveness of the products of the invention as viscosity index improvers is illustrated by the data in Table II. The results were ob- 8 tained in an acid-refined, Mid-Continent type base oil having an initial viscosity index 01' 80.6.

TABLE II X111. V15. compokmd l ilended ga g v I None 0. 0 30. 56 4- 84 80- 6 Product VIII 2- O 31- 98 5. O9 92- 5 Product XII 2. O 35. 03 5- 59 IUL 0 Product XIII 2 0 33.22 6.26 90. 3

The amount of the products 0! the invention to be incorporated in a. lubricating oil will vary with the particular oil and the application for which it is intended. Thus,'concentrations of from about 0.01 per cent to about 10 per cent may be used, although, generally, the desired results are obtained with concentrations of from .01 per cent to about 2 per cent. It is also contemplated that the products of the invention be incorporated in the oil in greater concentrations, i. e. above 10 per cent, to provide"concentrates for marketing, such concentrated compositions affording a readily soluble form of the additive materials for dilution with further quantities of oil prior to actual use.

The oils in which our new additive agents are incorporated, or the oil concentrate, may also contain other addition agents, designed to improve the character of the oil in other respects. such as corrosiveness, extreme pressure quality, detergency, etc.

Although the principles of this invention have been illustrated herein by means of certain specific examples and tests, it is not intended that the scope of the invention be limited thereby, but only as indicated in the following claims.

This application is a division of application Serial No. 127,267, filed November 14, 1949, now Patent No. 2,615,844, issued October 28, 1952.

I claim:

1. As a new composition of matter, the Product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of an aliphatic vinyl compound in the presence of from about 0.25 mole to about 6 moles of a thiophene compound selected from the grou consisting of thiophene and alkyl thiophenes, to form a thiophene-modified copolymer product and (2) reacting the copolymer product with a compound selected from the group consisting of (a) primary, normal, saturated, aliphatic alcohols having from about 12 to about 18 carbon atoms, (D) primary and secndary. saturated, aliphatic amines having from about 12 to about 18 carbon atoms and (c) a mixture, of primary, saturated, aliphatic amines containing from 8 to 18 carbon atoms and having an average of about 12 carbon atoms per molecule.

2. As a new composition of matter, the product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of an aliphatic vinyl ether in the presence of from about 0.25 mole to about 6 moles of thiophene, to form a thiophene-modified copolymer product and (2) esterifying the copolymer product with a primary, normal, saturated, aliphatic alcohol having from about 12 to about 18 carbon atoms.

3. As a new composition of matter, the product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of an aliphatic vinyl ester in the presence of from about 0.25 mole to about 6 moles'of thiophene, to form a thiophene-modified copolymer product and (2) esterifying the copolymer product with a primary, normal, saturated, aliphatic alcohol having from about 12 to about 18 carbon atoms.

4. As a new composition of matter, the product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of an aliphatic 1- olefin in the presence of from about 0.25 mole to about 6 moles of thiophene, to form a thicphene-modifled copolymer product and (2) esterifying the copolymer product with a primary, normal, saturated, aliphatic alcohol having from about 12 to about 18 carbon atoms.

5. As a new composition of matter, the product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of vinyl acetate in the presence of from about 0.25 mole to about 6 moles of 3-methy1 thiophene, to form a thiophene-modified copolymer product and (2) esterifying the copolymer product with lauryl a1- cohol.

6. As a new composition of matter, the product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of vinyl butyl ether in the presence of from about 0.25 mole to about 6 moles of thiophene, to form a thiophene-modi- 1o fled copolymer product and (2) esterifying the copolymer product with a mixture of'primary, normal, saturated, aliphatic alcohols having an average of about 14 carbon atoms per molecule.

7. As a new composition of matter, the Product obtained by (1) copolymerizing 1 mole of maleic anhydride with about 1 mole of octene-l in the presence of from about 0.25 mole to about 6 moles of thiophene, to form a thiophene-modified copolymer product and (2) esterifying the copolymer product with a mixture of primary, normal, saturated, aliphatic alcohols having an average of about 14 carbon atoms per molecule.

JOHN J. GIAMJVIARIA.

References Cited in the file of this patent UNITED STATES PATENTS 

1. AS A NEW COMPOSITION OF MATTER, THE PRODUCT OBTAINED BY (1) COPOLYMERIZING 1 MOLE OF MALEIC ANHYDRIDE WITH ABOUT 1 MOLE OF AN ALIPHATIC VINYL COMPOUND IN THE PRESENCE OF FROM 0.25 MOLE TO ABOUT 6 MOLES OF A THIOPHENE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THIOPHENE AND ALKYL THIOPHENES, TO FORM A THIOPHENE-MODIFIED COPOLYMER PRODUCT AND (2) REACTING THE COPOLYMER PRODUCT WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) PRIMARY, NORMAL, SATURATED, ALIPHATIC ALCHOLOS HAVING FROM ABOUT 12 TO ABOUT 18 CARBON ATOMS, (B) PRIMARY AND SECONDARY, SATURATED, ALIPHATIC AMINES HAVING FROM ABOUT 12 TO ABOUT 18 CARBON ATOMS AND (C) A MIXTURE OF PRIMARY, SATURATED, ALIPHATIC AMINES CONTAINING FROM 8 TO 18 CARBON ATOMS AND HAVING AN AVERAGE OF ABOUT 12 CARBON ATOMS PER MOLECULE. 